Effect of Fluid Convection on Dendrite Arm Spacing in Laser Deposition

Ni superalloys are widely used for hot section components in jet engines because they are very resistant to corrosion and maintain reasonably high strength at elevated temperature. However, the repair cost of the parts is high, partly due to the complexities of process variable optimization and control in laser cladding. In particular, optimizing the process parameters by experiments is time-consuming and costly. The microstructure and properties of the metal deposit are significantly influenced by values temperature gradient G and solidification rate R at the weld pool solidification boundary. Optimized values can help to reduce defects and improve properties of laser deposits. Optimization is hindered by the fact that the clad melt pool is hot and small, making in situ measurement of such solidification conditions difficult. Numerical simulation of the laser deposition process is a possible alternative to experimental measurement to obtain values of clad solidification parameters. In this investigation, G and R values at the weld pool solidification boundary were obtained from a three dimensional numerical simulation of laser deposition process and melt pool. The primary dendrite arm spacing and cooling rate of the deposited material were then correlated to these solidification conditions.     

Solidification paths of TiTaAl alloys

Microstructure evolution during solidification and high temperature phase equilibria were investigated for TiTaAl alloys in the vicinity of the 50 at.%Al isoconcentrate. Examination of dendrite morphologies and segregation profiles were used to deduce the phase sequencing during solidification and the boundaries of the relevant liquidi surfaces. In situ high-temperature X-ray diffraction and isothermal annealing experiments were conducted to determine the phases present at elevated temperatures and coupled with extensive characterization by transmission electron microscopy to elucidate the solid state transformations during cooling of the solidification microstructure. For approximately equiatomic TiAl, the primary phase selected from the liquid was α for the leaner Ta concentrations (< 7% Ta), as in the binary alloys of equivalent Al content, but changed to β with increasing Ta levels (> 10 %). With increasing Al and Ta the α liquidus penetrates deeply into the ternary. The interdendritic segregate was always γ. Dendrites of the β-forming alloys were heavily segregated leading to different microconstituents in the core and bulk dendrite regions during post-solidification cooling. In alloys with < 15 % Ta, (α₂ + γ_t) lath formed in the dendrite bulk due to the decomposition of α, with σ precipitating in the core (> 10% Ta). With increasing Ta levels the lath is gradually replaced by polycrystalline γ which grows into the dendrite bulk, and the core decomposes into a lamellar (γ + σ) microstructure from the decomposition of σ. The γ segregate does not transform further.     

Characterization of microstructure in laser-surface-alloyed layers of aluminum on nickel

In order to obtain basic understanding of microstructure evolution in laser-surface-alloyed layers, aluminum was surface alloyed on a pure nickel substrate using a CO₂ laser. By varying the laser scanning speed, the composition of the surface layers can be systematically varied. The Ni content in the layer increases with increase in scanning speed. Detailed cross-sectional transmission electron microscopic study reveals complexities in solidification behavior with increased nickel content. It is shown that ordered B2 phase forms over a wide range of composition with subsequent precipitation of Ni₂Al, an ordered ω phase in the B2 matrix, during solid-state cooling. For nickel-rich alloys associated with higher laser scan speed, the fcc γ phase is invariably the first phase to grow from the liquid with solute trapping. The phase reorders in the solid state to yield γ′ Ni₃Al. The phase competes with β AlNi, which forms massively from the liquid. The β AlNi transforms martensitically to a 3R structure during cooling in solid state. The results can be rationalized in terms of a metastable phase diagram proposed earlier. However, the results are at variance with earlier studies of laser processing of nickel-rich alloys.     

Evolution of interaction domain microstructure during spray deposition

An interaction domain, defined in the present article as the region where semisolid, atomized droplets impinge and are collected during spray atomization and deposition, was systematically investigated on the basis of a semisolid metal-forming mechanism. Accordingly, microstructural evolution in the interaction domain was rationalized by quantitative analyses of (1) the solid fraction of semisolid metal, (2) the extent of deformation and deformation strain rate, and (3) the solidification cooling rate. The results demonstrate that the fraction of solid in the interaction domain ranges from 0.5 to 0.8 for the materials studied here: Ni₃Al, Al-6 wt pct Si, and Al-6 wt pct Fe. Moreover, the results show that the semisolid material in the interaction domain experiences a severe deformation during deposition with an associated strain rate of up to 10⁶ s^-1. As a result of this deformation; the solidification structure is modified, and, in particular, any dendritic structure that is present will undergo extensive fragmentation. The severe deformation that is experienced by the interaction domain and the presence of a solidification cooling rate that is on the order of 10 to 10₅ Ks^-1 were proposed to be critical factors that promote the formation of a spheroidal grain morphology during spray atomization and deposition. Experimental support to this suggestion was provided by microstructural observations on Ni₃Al, Al-6Si, and Al-6Fe. In particular, the morphological modification of the primary Si phase that is observed in spray-atomized and spray-deposited Al-6Si was rationalized on the basis of these factors.     

Modeling of reactive atomization and deposition processing of Ni3Al

A recently developed processing technique for the synthesis of dispersion strengthened materials, reactive atomization and deposition (RAD), is introduced in the present paper. The unsteady state momentum, heat and mass transfer phenomena, including chemical reaction and phase change during RAD processing of molten Ni₃Al droplets with a N₂O₂ gas mixture, are numerically investigated. The effects of oxygen concentration in the atomization gas on gas characteristics, such as the compressibility of gas and heat-transfer coefficient, and on droplet characteristics, such as velocity, temperature, undercooling, cooling rate, and solidification history are determined. The surface cooling of droplets is simulated using a modified Newton's law of cooling. This improvement results in a good agreement between the calculated results and experimental measurements.     

Crystallization Behavior of Perovskite in the Synthesized High-Titanium-Bearing Blast Furnace Slag Using Confocal Scanning Laser Microscope

The isothermal phase composition of high-titanium-bearing slag (23 mass pct TiO₂) under an argon atmosphere during cooling process from 1723 K (1450 °C) was calculated by FactSage.6.3 (CRCT-ThermFact Inc., Montréal, Canada). Three main phases, which were perovskite, titania spinel, and clinopyroxene, could form during the cooling process and they precipitated at 1713 K, 1603 K, and 1498 K (1440 °C, 1330 °C, and 1225 °C), respectively. The nonisothermal crystallization process of perovskite in synthesized high-titanium-bearing slag was studied in situ by a confocal scanning laser microscope (CSLM) with cooling rate of 30 K/min. The results showed that the primary phase was perovskite that precipitated at 1703 K (1430 °C). The whole precipitation and growth process of perovskite was obtained, whereas other phases formed as glass under the current experimental conditions. Perovskite grew along a specific growth track and finally appeared with snowflake morphology. The growing kinetics of perovskite formation from molten slag were also mentioned.     

Directional Solidification and Liquidus Projection of the Sn-Co-Cu System

This study investigates the Sn-Co-Cu ternary system, which is of interest to the electronics industry. Ternary Sn-Co-Cu alloys were prepared, their as-solidified microstructures were examined, and their primary solidification phases were determined. The primary solidification phases observed were Cu, Co, Co₃Sn₂, CoSn, CoSn₂, Cu₆Sn₅, Co₃Sn₂, γ, and β phases. Although there are ternary compounds reported in this ternary system, no ternary compound was found as the primary solidification phase. The directional solidification technique was applied when difficulties were encountered using the conventional quenching method to distinguish the primary solidification phases, such as Cu₆Sn₅, Cu₃Sn, and γ phases. Of all the primary solidification phases, the Co₃Sn₂ and Co phases have the largest compositional regimes in which alloys display them as the primary solidification phases. There are four class II reactions and four class III reactions. The reactions with the highest and lowest reaction temperatures are both class III reactions, and are L + CoSn₂ + Cu₆Sn₅  =  CoSn₃ at 621.5 K (348.3 °C) and L + Co₃Sn₂ + CoSn = Cu₆Sn₅ at 1157.8 K (884.6 °C), respectively.     

3D Quantitative Characterization of Rapidly Solidified Al-36 Wt Pct Ni

The rapid solidification of a peritectic alloy is studied. Various 2D and 3D characterization techniques were effectively utilized to investigate the effect of cooling rate on both the phase fractions and the shrinkage porosity. Particles of Al-36 wt pct Ni were produced using a drop tube impulse system. Neutron diffraction and Rietveld analysis were used to quantify the phases formed during solidification. The microstructure of the produced particles was analyzed using SEM and X-ray microtomography. It was found that increasing cooling rate resulted in decreasing the Al₃Ni₂ to Al₃Ni ratio. Also, quantitative analysis of the microtomography images revealed that the volume percent of porosity increased with increasing particle size. The distribution of porosity was found to be significantly different in small and large particles. It was concluded that the extensive growth of Al₃Ni₂ at lower cooling rates followed by the peritectic reaction made the feeding of the shrinkages more difficult, and as a result, the volume percent of porosity increased. Other findings showed that high cooling rate during solidification would result in the formation of a quasicrystalline phase, known as D-phase, and suppression of the primary Al₃Ni₂. Also, investigation of the 3D structure of the solidified particles revealed that large particles of Al-36 wt pct Ni contain multiple nucleation sites, while smaller particles contain only one single nucleation site.     

Analysis of heat flow and microstructure evolution during spray deposition of Fe-3C-1.5Mn alloy

A theoretical model for the concomitant solidification of droplets and preform during spray deposition has been proposed, based on heat-flow analysis. It has been unambiguously demonstrated that cooling rates approaching those in the rapid solidification (RS) regime can only be achieved when the droplets are still in free flight during the deposition process. The cooling rates in the droplets range from 10⁴–10⁶ Ks^?1 depending upon their size for the experimental conditions employed in the present studies. In contrast, the model predicted cooling rates for the deposits in the region of 10³–10⁴ Ks^?1. A hypoeutectic Fe-3C-1.5Mn-0.3Si has been chosen as an experimental alloy for studies relating to microstructural characterization. The microstructure of powder developed fully during solidification of droplets in free flight revealed dendritic morphology of the metastable austenitic phase, whereas the spray-deposited alloy exhibited characteristic homogeneous and refined substructure. The evolution of microstructure during spray deposition as also during atomization has been compared and discussed by invoking the proposed model.     

Microstructures of rapidly-solidified binary TiAl alloys

The microstructures of rapidly-solidified binary TiAl alloys containing 46–70 at.% Al have been studied using optical and analytical transmission electron microscopy (AEM). The phases present in the alloys and their distribution were found to be a sensitive function of composition. Essentially single-phase microstructures were seen for alloys with 46 at.% Al, 50–52 at.% Al and 60–65 at.% A. The primary solidification phases present in these alloys were α-Ti, ordered γ-TiAl and disordered cubic TiAl, respectively. The 60–65 at.% Al alloys showed indications of the solid-state formation of long-period superlattice structures based upon γ-TiAl, due to the excess Al. In other composition ranges, two-phase microstructures were seen. The 48 at.% Al alloy contained α₂-Ti₃Al + γ-TiAl, with α₂-Ti₃Al as the primary solidification phase. Alloys from 53 to 55 at.% Al were also α₂-Ti₃Al + γ-TiAl, but with γ-TiAl as the primary solidification phase. The 70 at.% Al alloy was two phase TiAl₂ + TiAl₃. A strong effect of interstitial oxygen content on the α₂-Ti₃Al + γ-TiAl phase relations was also seen. Comparison of these results with the equilibrium phase diagram and with ingot studies of the same alloys showed that most of the microstructures produced by rapid solidification were metastable. A possible metastable phase diagram for TiAl which is consistent with the results is proposed.     

Iron intermetallic phases in the Al corner of the Al-Si-Fe system

The iron intermetallics observed in six dilute Al-Si-Fe alloys were studied using thermal analysis, optical microscopy, and image, scanning electron microscopy/energy dispersive X-ray, and electron probe microanalysis/wavelength dispersive spectroscopy (EPMA/WDS) analyses. The alloys were solidified in two different molds, a preheated graphite mold (600°C) and a cylindrical metallic mold (at room temperature), to obtain slow (}0.2 °C/s) and rapid (}15 °C/s) cooling rates. The results show that the volume fraction of iron intermetallics obtained increases with the increase in the amount of Fe and Si added, as well as with the decrease in cooling rate. The low cooling rate produces larger-sized intermetallics, whereas the high cooling rate results in a higher density of intermetallics. Iron addition alone is more effective than either Si or Fe+Si additions in producing intermetallics. The alloy composition and cooling rate control the stability of the intermetallic phases: binary Al-Fe phases predominate at low cooling rates and a high Fe:Si ratio; the β-Al₅FeSi phase is dominant at a high Si content and low cooling rate; the α-iron intermetallics (e.g., α-Al₈Fe₂Si) exist between these two; while Si-rich ternary phases such as the δ-iron Al₄FeSi₂ intermetallic are stabilized at high cooling rates and Si contents of 0.9 wt pct and higher. Calculations of the solidification paths representing segregations of Fe and Si to the liquid using the Scheil equation did not conform to the actual solidification paths, due to the fact that solid diffusion is not taken into account in the equation. The theoretical models of Brody and Flemings^[44] and Clyne and Kurz^[45] also fail to explain the observed departure from the Scheil behavior, because these models give less weight to the effect of solid back-diffusion. An adjusted 500°C metastable isothermal section of the Al-Si-Fe phase diagram has been proposed (in place of the equilibrium one), which correctly predicts the intermetallic phases that occur in this part of the system at low cooling rates (}0.2 °C/s).     

Iron intermetallic phases in the Al corner of the Al-Si-Fe system

The iron intermetallics observed in six dilute Al-Si-Fe alloys were studied using thermal analysis, optical microscopy, and image, scanning electron microscopy/energy dispersive X-ray, and electron probe microanalysis/wavelength dispersive spectroscopy (EPMA/WDS) analyses. The alloys were solidified in two different molds, a preheated graphite mold (600 °C) and a cylindrical metallic mold (at room temperature), to obtain slow (∼0.2 °C/s) and rapid (∼15 °C/s) cooling rates. The results show that the volume fraction of iron intermetallics obtained increases with the increase in the amount of Fe and Si added, as well as with the decrease in cooling rate. The low cooling rate produces larger-sized intermetallics, whereas the high cooling rate results in a higher density of intermetallics. Iron addition alone is more effective than either Si or Fe+Si additions in producing intermetallics. The alloy composition and cooling rate control the stability of the intermetallic phases: binary Al-Fe phases predominate at low cooling rates and a high Fe:Si ratio; the β-Al₅FeSi phase is dominant at a high Si content and low cooling rate; the α-iron intermetallics (e.g., α-Al₈Fe₂Si) exist between these two; while Si-rich ternary phases such as the δ-iron Al₄FeSi₂ intermetallic are stabilized at high cooling rates and Si contents of 0.9 wt pct and higher. Calculations of the solidification paths representing segregations of Fe and Si to the liquid using the Scheil equation did not conform to the actual solidification paths, due to the fact that solid diffusion is not taken into account in the equation. The theoretical models of Brody and Flemings^[44] and Clyne and Kurz^[45] also fail to explain the observed departure from the Scheil behavior, because these models give less weight to the effect of solid back-diffusion. An adjusted 500 °C metastable isothermal section of the Al-Si-Fe phase diagram has been proposed (in place of the equilibrium one), which correctly predicts the intermetallic phases that occur in this part of the system at low cooling rates (∼0.2 °C/s).     

On the influence of in-situ reactions on grain size during reactive atomization and deposition

A fundamental study of the factors that govern grain size of 5083 Al processed via reactive atomization and deposition (RAD) is reported. Microstructural observation shows that the average grain size in RAD 5083 Al is slightly smaller than that in the material processed via N₂ spray deposition (SDN). A numerical approach, together with measurements of the temperature histories inside the deposited materials, is implemented to analyze the influence of in-situ reactions during RAD process on the evolution of grain size. The numerical results show that RAD 5083 Al possesses a slightly higher density of nuclei relative to that present in SDN 5083 Al on a per unit volume of deposited material basis at the beginning of the slow solidification of remaining liquid phase. Furthermore, the RAD material exhibits a slightly lower coarsening extent during the slow solidification. Grain growth is negligible during the solid-phase cooling. Accordingly, the calculated grain size in RAD 5083 Al is slightly smaller than that in SDN 5083 Al, consistent with the observed results.     

Viscosity and nonequilibrium solidification of Co-P melts

The concentration dependences of the viscosity and solidification of Co-P melts containing from 16 to 25 at % P are studied by viscosimetry, differential thermal analysis, and metallography. A maximum near 20 at % P in the concentration dependence of the viscosity is observed for the first time. The maximum is associated with a composition short-range Co₄P-type order present in this composition range. On cooling the melts at rates of 20–100 K/min in the concentration range from 18 to 22 at % P, a metastable phase with a composition close to the eutectic composition (20 at % P) can form. This metastable phase decomposes on cooling to form equilibrium phases (Co and Co₂P).     

Effects of Solidification Conditions on Grain Refinement Capacity of TiC in Directionally Solidified Ti6Al4V Alloy

In this study, the effects of solidification conditions on the grain refinement capacity of heterogeneous nuclei TiC in directionally solidified Ti6Al4V alloy were investigated using experimental and numerical approaches. Ti6Al4V powder with and without TiC particles in a Ti6Al4V sheath was melted and directionally solidified at various solidification rates via the floating zone melting method. In addition, by using the phase field method, the microstructural evolution of directionally solidified Ti6Al4V was simulated by varying the temperature gradient G and solidification rate V. As the solidification rate increased, the increment of the prior β grain number by TiC addition also increased. There are two reasons for this: first, the amount of residual potent heterogeneous nuclei TiC is larger. Second, the amount of TiC particles that can nucleate becomes larger. This is because increasing the constitutional undercooling ΔT_c leads to the activation of a smaller radius of heterogeneous nuclei and a higher nucleation probability from each radius. At a cooling rate R higher than that in the floating zone melting experiment (R = 3 to 1000 K/s), the maximum degree of constitutional undercooling ΔT_c,Max has a peak value, which suggests that constitutional undercooling ΔT_c has a smaller contribution at higher cooling rates, such as those that occur during electron beam melting (EBM), including laser powder bed fusion (LPBF).

     

Direct laser deposition of a single-crystal Ni<Subscript>3</Subscript>Al-based IC221W alloy

Single-crystal (SX) nickel aluminide alloys have potential for structural applications where high-temperature strength and oxidation resistance are required. In this work, SX deposits of the Ni₃Al-based IC221W alloy were produced on a SX Ni-base superalloy substrate by means of the laser-engineered net shaping (LENS) process. The microstructure of the deposits was characterized. The effects of processing parameters on the SX solidification in the melt pool and on the fabricability by LENS were investigated. A simple relationship between the ratio of the temperature gradient to the growth velocity and the processing parameters was derived, which can be used qualitatively to guide the proper selection of processing conditions to maintain the columnar dendritic growth during the laser deposition. On the basis of analyses and experiments, the effects of processing parameters on the susceptibility to stray grain formation and solidification cracking are discussed.     

Solidification of undercooled Sn-Sb peritectic alloys: Part II. Heterogeneous nucleation

The undercooling behavior of fine droplet samples of Sn-rich, Sn-Sb alloys was investigated using differential thermal analysis (DTA). Undercooling levels measured during cooling from the liquid state follow the trend of the intermetallic phase liquidus, suggesting that solidification of all droplet samples (even those which solidify to yield a supersaturatedβ-tin product) was probably initiated with formation of primary intermetallic phase. Heterogeneous nucleation thermal cycling treatments were then used to measure the relative catalytic potency of primary intermetallic phases in this system for nucleation ofβ-tin during cooling. Crystallization reactions below the equilibrium peritectic temperature of 250 °C, at 187 °C and 230 °C, have been interpreted as corresponding to nucleation ofβ on Sn₃Sb₂ and SnSb substrates, respectively. The behavior observed in the Sn-Sb system can be generalized to guide the interpretation of heterogeneous catalysis and the analysis of solidification pathways in other peritectic alloy systems. Formerly Graduate Student, Department of Materials Science and Engineering, University of Wisconsin-Madison     

In Situ Observation of P91 High-Alloy Steel Solidification Characteristics at Different Cooling Rates

To clarify the effect of different radial cooling intensities on the formation of central cracks in large round bloom continuous casting, it is necessary to study the solidification characteristics and dynamics of P91 high-alloy steel at different cooling rates (CRs) to improve the central defects. In this article, the solidification characteristics of P91 high-alloy steel at different CRs are studied by using the Thermo-Calc software, high-temperature laser confocal microscopy, scanning electron microscopy, and optical microscopy. Meanwhile, the growth kinetics of δ-Fe and γ-Fe phases under different CRs are determined. The results show that the solidification path of P91 high-alloy steel is L(L + δ-Fe) → (L + γ-Fe + δ-Fe) → (δ-Fe + γ-Fe). The δ-Fe and γ-Fe phase precipitation process is divided into two stages. Stage I is the nucleation and rapid growth phase, in which a high undercooling is required. Stage II is the slow growth stage, where the undercooling decreases and remains constant. The initial growth linear velocities of the δ-Fe phase are 0.51, 2.72, and 2.09 μm s⁻¹ at CRs of 10, 50, and 100 °C min⁻¹, respectively, while those of the γ-Fe phase are 0.10, 1.42, and 1.41 μm s⁻¹.